Manufacture of ethyl acetate



- ture of Ethyl Patented June 2, i923.

MABTINMUGDAN AND WILL! HERRMANN, OF NUREMBERG, GERMANY, ASSIGNORS GERMANY.

.MANUFACTURE or ETHYL ACETATE.

No Drawing.

To all whom it may concern.

WILLY HERRMANN, subjects of the German Emperor, residing at Nuremberg, in the Empire of Germany, have invented certain new and useful Im rovements in the Manufaccetate, of'which the followin is a specification.

Tt is known that the transformation of aliphatic aldehydes into the I corresponding fatty acid esters, e. g. of ac ldehyde into ethyl acetate, can beeifected by the action of ploying acetaldehyde he obtained yields up aluminium alcoholate. This polymerization of aldehyde has been recently closely investigated b Tischtschenko (Journ. Russ. Phys. Chem. es. 388, p. 398-418; Chem. Centralblatt 1906 11. p. 1309), who employed a pure distilled aluminium alcoholate. When emto about 70% of ethyl acetate but in order to obtain this yield he had to employ considerable quantities of the catalyst, namely 15% and moreover the reaction required at least several days but usually weeks or months. p

, Now we have discovered the surprising fact that it is possible to obtain an almost quantitative yield of ethyl acetate with very considerably smaller quantities of catalyst and that moreover the ve long reactiontime can be very considera ly shortened if aluminium alcoholate is'employed as cont, densing agent in conjunction with a subalcoholate by the stance containin a halogen. These substances must obviously be employed only in such amounts that their own characteristic polymerizin action does not take place or onl takes p ace to a very small extent.

e prefer employing the haloge'nides or other halogeniferous' compounds of metals These additions may be conveniently melted with the aluminium alcoholate but they may also be incorporated inany other suitable manner. For instance iodine in the elementary form can be added previously in preparin method of Gladstone and Tribe (Jahresber, llber die lFortschr. d.

Qhemie 1876, p. 329 and the crude alcoholate containing io ine may be employed forthwith without further rectification.

Ewmmple 1.

Six parts of an aluminium alcoholate containing chlerine, obtained. by melting with Application filed. lflovember 26, 1913. Serial No. 803,279.

about 10% of aluminium chloride, are added as a powder to 135 parts of acetaldehyde, with efficient stirring and cooling. After a reaction of several hours 123 parts were distilled off giving an almost pure acetic ester fraction.

Example 2.

To 100 parts of cooled aldehyde contained in a vessel provided with stirring gear are added four parts of aluminium alcoholate product which was produced by treating aluminium alcoholate with water and melting in vacuo so that it contains 21% alu minium. The heat of reaction is removed by cooling and stirring continued for several hours. After the reaction is over, the product is distilled off and 87% of acetic ester is obtained.

The above mentioned catalysts can be applied both in the solid state and also in the dissolved form. In fact it has been found that the catalysts obtained by melting aluminium alcoholate'with a substance containing a halogen are soluble in solvents such as ethyl acetate and indeed to a greater extent than pure aluminium alcoholate. These solutions are of advantage in so far as the catalysts and the aldehyde form one phase and are therefore in an ideal state of distribution, while in two phase systems there T0 CONSORTIUM FUR ELEKTROCHEMISCHE INDUSTRIE G. M. B. 115., OF NUREMBERG,

is a danger arising from ready over-heatin either be added to the aldehyde or vice versa the aldehyde may be allowed to flow gradually into the solution. Finally it is possible toadmix the solvent with the aldehyde ab initio and to introduce the solid catalyst into this mixture when complete or partial solution soon takes place.

We claim:

l. The process of making ethyl acetate which comprises bringing acetaldehyde in contact with aluminum alcoholate and a substance containing a halogen.

which comprises treating aluminum alcoholate with aluminum chloride and causing the product resulting from such treatment to act upon acetaldehyde. U

4. The process of making ethyl acetate which comprises melting aluminum alcoholate with aluminum chloride and causing the product resulting from such treatment to act upon acetaldehyde.

5. he process of making ethyl acetate which comprises treating aluminum alcoholatewith a substance containing'a halogen and causing the product resulting from such treatment to act upon acetaldehyde in the presence-of .a solvent capable of dissolving said i roduct.

6. he process of making ethyl acetate which comprises treating aluminum alcoholate with aluminum chloride and causing the product resulting from such treatment to act upon acetaldehyde in the presence of a solvent capable of dissolving said product. I

7. The process of making ethyl acetate which comprises treating aluminum alcoholate with a substance containing a halogen and causing the product resulting from such treatment to act upon acetaldehyde in the presence of" ethyl acetate. 7

8. The process of making ethyl acetate which comprises treating aluminum alcoholate with aluminum chloride and causing the product resulting from such treatment to act upon acetaldehyde in the presence of ethyl acetate.

9. The proces of making ethyl acetate which comprises bringing acetaldehyde in contact with aluminum alcoholate and a sub- .in ethyl acetate an stance containing a halogen in the presence of a'solvent.

10. The process of making ethyl acetate which comprises treating aluminum alcoholate with a substance containing a halogen, dissolving the product resulting from such treatment in an indifferent organic solvent and causing the solution thus obtained to act upon acetaldehyde,

11. The process of'making ethyl acetate which comprises treating aluminum alcoholate with aluminum chloride dissolving the product resulting from such treatment in an indifferent organic solvent and causing the solution thus obtained to act upon acetaldehyde.

12. The process of making ethyl acetate which comprises treating aluminum alcoholate with a substance containing a halogen, dissolving the product resulting from such treatment in ethyl acetate and causing the solution thus obtained to act upon acetaldehyde.

13. The process of making ethyl acetate which comprises treating aluminum alcoholate with aluminum chloride, dissolving the product resultin from such treatment causing the solution thus obtained to act, upon acetaldehyde.

In testimony whereof We aflix our signatures in presence of two witnesses.

DR. MARTIN MUGDAN. QR. WILLY' HERRMANN. Witnesses:

MARTIN ERHARD, Enron BAUM. 

